CN113540390A - Preparation method and application of dynamic interface coating of metal zinc cathode of zinc ion battery - Google Patents
Preparation method and application of dynamic interface coating of metal zinc cathode of zinc ion battery Download PDFInfo
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Abstract
A preparation method and application of a dynamic interface coating of a metal zinc cathode of a zinc ion battery belong to the technical field of energy materials. According to the invention, the interface layer which dynamically adapts to the change of the interface volume is modified on the surface of the metal zinc cathode of the zinc ion battery by a spin coating method, and the synthesized polymer PDMS has extremely high viscoelastic property and shows higher dynamic adaptability. Prepared TiO2‑xContains abundant oxygen vacancy. The prepared dynamic interface coating can be applied to a water-based zinc ion battery. The invention prepares PDMS/TiO with dynamic self-adaptive volume change2‑xInterfacial coating, the change of dynamic buffer volume inhibits dendritic crystal growth, and simultaneously induces Zn through abundant oxygen vacancies2+Fast and uniform transfer to further improve the ionic conductivity of the interface layer so as to stabilize Zn goldAnd the surface is covered, so that the utilization rate and the cycle life of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a preparation method and application of a dynamic interface coating of a metal zinc cathode of a zinc ion battery.
Background
Nowadays, economy and science and technology are rapidly improved, and the dependence of society on available energy is increasing day by day. The reserves of traditional primary energy sources such as natural gas, coal and petroleum are gradually exhausted, and the direct combustion of fossil fuels leads to deepening of greenhouse effect and obvious environmental problems. Therefore, new energy systems such as solar energy, wind energy, geothermal energy, and tidal energy have been widely studied. However, these new energy sources have a large fluctuation and a disadvantage of being unable to continuously generate electricity, compared with fossil energy, and thus, their large-scale and long-term use is limited. Therefore, the development of efficient energy storage systems is a need to address new energy applications and the development of human society. The most fundamental criteria for developing an ideal large energy storage system are low cost, high reliability, good safety, environmental friendliness, high efficiency, long cycle life, and high energy density.
Lithium ion batteries have been receiving attention since their commercial development, and due to their high energy density and long cycle life, have dominated secondary battery applications for nearly 30 years. However, the lithium ion battery using a flammable organic electrolyte has serious problems of environmental pollution and poor safety, and the supply of lithium is seriously in short supply. Therefore, aqueous zinc ion batteries are a strong competitor for future large-scale electrical energy storage applications by virtue of cost-effectiveness, environmental friendliness, safety and competitive energy density. Despite the enormous potential of zinc metal cathodes, their recharging is poor due to dendrite formation and insufficient coulombic efficiency for deposition/stripping, which to some extent prevents practical large-scale applications. Since zinc has very high mechanical properties, its young's modulus is much higher than that of lithium and sodium, which means that zinc dendrites, once formed in large scale, can easily penetrate through the separator to grow, resulting in cell failure. Dendrite formation, low deposition/exfoliation coulombic efficiency and poor cycling stability of zinc cathodes remain obstacles to their use.
Therefore, it is very critical to optimize the material and structural design of the zinc anode. With the continuous breakthrough of the related technology in the field of nano materials in recent years, researchers have proposed many new methods to inhibit the growth of zinc dendrites, so as to hopefully stabilize the metal zinc cathode, improve the reversible use efficiency of active zinc, and further improve the long-period cycle life of the battery, thereby obtaining a high-efficiency, safe and high-energy-density energy storage system. The zinc cathode system without dendrites and with high stability is constructed, and a safe and efficient metal zinc cathode is developed, so that the zinc cathode is stable in the working process, and the zinc cathode system has great significance for constructing a new energy storage system.
Disclosure of Invention
The invention provides a preparation method and application of a dynamic interface coating of a metal zinc cathode of a zinc ion battery, aiming at the problems of volume expansion of a cathode interface, low coulombic efficiency and cycle life attenuation caused by dendritic crystal growth of the zinc metal cathode.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a dynamic interface coating of a metal zinc cathode of a zinc ion battery comprises the following steps:
step one, adding boric acid into dimethyl silicone oil, stirring and mixing uniformly at a high speed, then adding ferric chloride, and preparing PDMS through catalytic crosslinking at a high temperature;
step two, TiO 22At the temperature of 400-450 ℃, the volume ratio of argon to hydrogen is 95: 5 to obtain oxygen-containing defective TiO2-x；
Step three, dissolving the prepared PDMS in a volatile ether organic solvent, and then adding organic salt Zn (TFSI)2；
Step four, preparing the oxygen-containing defective TiO2-xAdding into the third solution, oxygen-containing defective TiO2-xThe mass ratio of the solution to the solution in the third step is 2-15%, and the solution is stirred and mixed evenly at a high speed;
fifthly, polishing the surface of the zinc foil by using sand paper, and then cleaning the zinc foil by using deionized water and ethanol;
step six, dropwise adding the mixture obtained in the step four onto the zinc foil processed in the step five for spin coating to form a film, and preparing a zinc foil pole piece with a spin coating interface layer, wherein the thickness of the spin coating is 2-50 microns;
and step seven, drying the zinc foil coated with the interface layer obtained in the step six at room temperature, and removing the volatile solvent.
The dynamic interface coating obtained by the method is applied to the protection of the metal zinc cathode of the zinc ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention constructs PDMS/TiO with dynamic self-adaptive volume change2-xInterfacial coating, the change of dynamic buffer volume inhibits dendritic crystal growth, and simultaneously induces Zn through abundant oxygen vacancies2+The ionic conductivity of the interface layer is further improved by rapid and uniform transfer so as to stabilize the Zn metal surface, thereby improving the utilization rate and cycle life of the battery;
(2) the PDMS prepared by the invention has hydrophobic property, can effectively avoid the corrosion of water-based electrolyte to zinc foil, and can prolong the service life of the electrode;
(3) the raw materials adopted by the invention are simple and easy to obtain, the price is low, and the invention has the potential of large-scale use;
(4) the zinc cathode protected by the dynamic coating has good cycling stability and safety performance, and the preparation process is clean and environment-friendly and is simple to operate.
Drawings
FIG. 1 is an oxygen deficient TiO prepared in example 12-xTransmission electron microscopy images of (a);
FIG. 2 shows that the zinc symmetrical cell prepared in example 1 has a concentration of 1mAcm-2、1mAh cm-2Voltage-time curve under test conditions;
FIG. 3 shows the zinc/titanium foil half cell prepared in example 1 at 0.5mAcm-2、0.5mAh cm-2Coulombic efficiency curves under the test conditions.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
According to the invention, the interface layer which dynamically adapts to the change of the interface volume is modified on the surface of the metal zinc cathode of the zinc ion battery by a spin coating method, and the synthesized polymer PDMS has extremely high viscoelastic property and shows higher dynamic adaptability. Prepared TiO2-xContains abundant oxygen vacancy. The prepared dynamic interface coating can be applied to a water-based zinc ion battery. The invention prepares PDMS/TiO with dynamic self-adaptive volume change2-xInterfacial coating, the change of dynamic buffer volume inhibits dendritic crystal growth, and simultaneously induces Zn through abundant oxygen vacancies2+The rapid and uniform transfer further improves the ionic conductivity of the interface layer to stabilize the Zn metal surface, thereby improving the utilization rate and the cycle life of the battery.
The first embodiment is as follows: the embodiment describes a preparation method of a dynamic interface coating of a metal zinc cathode of a zinc ion battery, which comprises the following steps:
step one, adding boric acid into dimethyl silicone oil, stirring and mixing uniformly at a high speed, then adding ferric chloride, and preparing PDMS through catalytic crosslinking at a high temperature;
step two, TiO 22At the temperature of 400-450 ℃, the volume ratio of argon to hydrogen is 95: 5 to obtain oxygen-containing defective TiO2-x；
Step three, dissolving the prepared PDMS in a volatile ether organic solvent, and then adding organic salt Zn (TFSI)2；
Step four, preparing the oxygen-containing defective TiO2-xAdding into the third solution, oxygen-containing defective TiO2-xThe mass ratio of the solution to the solution in the third step is 2-15%, and the solution is stirred and mixed evenly at a high speed;
fifthly, polishing the surface of the zinc foil by using sand paper, and then cleaning the zinc foil by using deionized water and ethanol;
step six, dropwise adding the mixture obtained in the step four onto the zinc foil processed in the step five for spin coating to form a film, and preparing a zinc foil pole piece with a spin coating interface layer, wherein the thickness of the spin coating is 2-50 microns;
and step seven, drying the zinc foil coated with the interface layer obtained in the step six at room temperature, and removing the volatile solvent.
Step eight, assembling the zinc foil spin-coated with the interface layer into a battery, and testing the performance; the universal test condition for testing the current density is 0.01-10 mAcm-2。
The second embodiment is as follows: in the first step, the high temperature is 180-220 ℃, the crosslinking reaction cannot occur at too low temperature, and the preparation is not facilitated at too high temperature.
The third concrete implementation mode: in a first step of the preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery, the addition ratio of the boric acid, the simethicone and the ferric chloride is 0.1-1 g: 1mL of: 0.01 g.
The fourth concrete implementation mode: in the second step, the temperature of the heat treatment is 250-450 ℃, the time is 0.5-5H, and Ar/H is used2(95%/5%) H in the atmosphere2Oxygen can be reduced to produce uniform oxygen defects.
The fifth concrete implementation mode: in a third step of the preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery, the volatile ether organic solvent is one or more of diethyl ether, tetrahydrofuran, diethylene glycol monomethyl ether, propylene glycol methyl ether and dipropylene glycol dimethyl ether. The ether reagent is easy to volatilize, which is beneficial to spin coating, and can effectively dissolve the crosslinking PDMS, and the property of the volatilized PDMS is not changed.
The sixth specific implementation mode: in the third step, the organic salt Zn (TFSI)2The mass ratio of the raw materials to PDMS is 1: 3.
the seventh embodiment: a method for preparing a dynamic interface coating of a zinc negative electrode of a zinc ion battery, according to a sixth specific embodiment, the method comprisesThe spin coating speed is 500 rpm-1-3500r min-1。
The specific implementation mode is eight: the dynamic interface coating obtained by the method of any one of the first to seventh embodiments is applied to the protection of a zinc negative electrode of a zinc ion battery metal.
Example 1:
0.6g of boric acid is added into 5ml of dimethyl silicone oil, stirred at a high speed for 2 hours and mixed uniformly. Then 0.01g of ferric chloride is added while slowly heating to 185 ℃ and stirring for 1 hour, then heating to 210 ℃ for catalytic crosslinking until solidification, and cooling to room temperature to prepare the PDMS. 1.5g PDMS was dissolved in 1ml tetrahydrofuran and 0.5g Zn (TFSI) was added2Stirring is continued. Purchased industrially produced TiO2Ar/H at 400 ℃2(95%/5%) for 2 hours to give TiO2-x. Adding 4% TiO into 5ml solution2-xPreparing PDMS/TiO2-x. Polishing the surface of the zinc foil by using sand paper, and then cleaning the surface of the zinc foil by using deionized water and ethanol; taking PDMS/TiO2-xDripping the zinc foil on a zinc foil for spin coating to form a film, and preparing a zinc foil pole piece with a spin coating interface layer, wherein the thickness of the spin coating is 2-50 microns; the resulting zinc foil coated with the interface layer was dried at room temperature to remove the volatile solvent. 1mol L-1The zinc sulfate is dissolved in deionized water to be used as electrolyte. The electrolyte and the metal zinc sheet are assembled into a battery with 0.5mAcm-2，0.5mAh cm-2Under the test condition, the coulombic efficiency is as high as 98%. In a symmetrical zinc | zinc battery system, at 1mAcm-2、1mAh cm-2Under the test conditions, the polarization voltage did not change over a long period of time, showing a long cycle life.
FIG. 1 shows the oxygen-deficient TiO prepared in this example2-xFIG. 1 shows a transmission electron micrograph of TiO2-xThe particles were uniform and about 10nm in size.
FIG. 2 shows that the zinc symmetrical cell prepared in example 1 has a concentration of 1mAcm-2、1mAh cm-2Under the test condition, the voltage-time curve graph shows that the polarized voltage has no obvious change within 500 hours;
FIG. 3 shows Zn/Ti prepared in example 1Foil half cell at 0.5mAcm-2、0.5mAh cm-2Under the test condition, the coulombic efficiency curve chart still achieves 98 percent after circulating for 300 times.
Example 2:
adding 1g of boric acid into 5ml of dimethyl silicone oil, stirring at a high speed for 2 hours, and uniformly mixing. Then 0.01g of ferric chloride was added while slowly heating to 185 ℃ and stirring for 1 hour, then heating to 210 ℃ to catalytically crosslink until solidification, and cooling to room temperature to prepare PDMS. 1.5g PDMS was dissolved in 3ml diethyl ether and 0.5g Zn (TFSI) was added2Stirring is continued. Purchased industrially produced TiO2Ar/H at 450 ℃2(95%/5%) for 2 hours to give TiO2-x. Adding 4% TiO into 5ml solution2-xPreparing PDMS/TiO2-x. Polishing the surface of the zinc foil by using sand paper, and then cleaning the surface of the zinc foil by using deionized water and ethanol; taking PDMS/TiO2-xDripping the zinc foil on a zinc foil for spin coating to form a film, and preparing a zinc foil pole piece with a spin coating interface layer, wherein the thickness of the spin coating is 2-50 microns; the resulting zinc foil coated with the interface layer was dried at room temperature to remove the volatile solvent. 1mol L-1The zinc trifluoromethanesulfonate is dissolved in deionized water to serve as an electrolyte. And assembling the electrolyte and a metal zinc sheet into a battery, and testing electrochemical data.
Claims (8)
1. A preparation method of a dynamic interface coating of a metal zinc cathode of a zinc ion battery is characterized by comprising the following steps: the method comprises the following steps:
step one, adding boric acid into dimethyl silicone oil, stirring and mixing uniformly at a high speed, then adding ferric chloride, and preparing PDMS through catalytic crosslinking at a high temperature;
step two, TiO 22At the temperature of 400-450 ℃, the volume ratio of argon to hydrogen is 95: 5 to obtain oxygen-containing defective TiO2-x；
Step three, dissolving the prepared PDMS in a volatile ether organic solvent, and then adding organic salt Zn (TFSI)2；
Step four, preparing the oxygen-containing defective TiO2-xAdding the mixture into the solution obtained in the third step,oxygen-containing deficient TiO2-xThe mass ratio of the solution to the solution in the third step is 2-15%, and the solution is stirred and mixed evenly at a high speed;
fifthly, polishing the surface of the zinc foil by using sand paper, and then cleaning the zinc foil by using deionized water and ethanol;
step six, dropwise adding the mixture obtained in the step four onto the zinc foil processed in the step five for spin coating to form a film, and preparing a zinc foil pole piece with a spin coating interface layer, wherein the thickness of the spin coating is 2-50 microns;
and step seven, drying the zinc foil coated with the interface layer obtained in the step six at room temperature, and removing the volatile solvent.
2. The preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery according to claim 1, characterized in that: in the first step, the high temperature is 180-220 ℃.
3. The preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery according to claim 1, characterized in that: in the first step, the adding proportion of the boric acid, the dimethyl silicone oil and the ferric chloride is 0.1-1 g: 1mL of: 0.01 g.
4. The preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery according to claim 1, characterized in that: in the second step, the temperature of the heat treatment is 250-450 ℃, and the time is 0.5-5 h.
5. The preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery according to claim 1, characterized in that: in the third step, the volatile ether organic solvent is one or more of diethyl ether, tetrahydrofuran, diethylene glycol monomethyl ether, propylene glycol methyl ether and dipropylene glycol dimethyl ether.
6. The preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery according to claim 1, characterized in that: in step three, the organic salt Zn (TFSI)2The mass ratio of the raw materials to PDMS is 1:3。
7. the preparation method of the dynamic interface coating of the metal zinc cathode of the zinc ion battery according to claim 1, characterized in that: in the sixth step, the spin coating rotating speed is 500rmin-1-3500rmin-1。
8. The dynamic interface coating obtained by the method of any one of claims 1 to 7 is applied to the protection of a metal zinc cathode of a zinc ion battery.
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| CN114628681A (en) * | 2022-03-20 | 2022-06-14 | 青岛科技大学 | Preparation method of macromolecular polyphenol zinc complex as zinc cathode protective layer |
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